CN100510036C - Organic molybdenum lube oil additive and production thereof - Google Patents

Abstract

An organic molybdenum lube oil additive and its production are disclosed. It is prepared by reacting for mixture of two or above substances of ethyl-phenalkyl acid polybasic alcohol ester, inorganic molybdenum compound, aliphatic amine, arylamine, mixed amine and acylamide. It has excellent wear-resisting performance.

Description

A kind of organic molybdenum lubricating oil additive and preparation method thereof

technical field

The invention relates to a lubricating oil additive and a preparation method thereof, more specifically, the invention relates to an organic molybdenum lubricating oil additive and a preparation method thereof.

Background technique

With the increasingly stringent environmental regulations and the increasing requirements for energy saving, engine manufacturers continue to reduce the size of the engine, increase the compression ratio, and increase the operating temperature of the engine, thereby improving fuel utilization, saving energy and reducing exhaust emissions. At the same time, lubricating oil is also required to have good anti-wear and anti-friction properties. All of these put forward higher requirements on the anti-wear, anti-friction and anti-oxidation performance of lubricating oil.

Phosphorus in lubricating oil will shorten the effective life of catalysts in automobile exhaust converters. Sulfur in lubricating oil is incompatible with elastomeric seals and is corrosive, so organic molybdenum additives without sulfur and phosphorus can be applied to high-level , High specification lubricating oil, has wider applicability.

US Patent No. 4,692,256 discloses an organic molybdenum lubricating oil additive with anti-wear, anti-friction and anti-oxidation properties.

U.S. Patent No. 4,889,647 discloses an organic molybdenum lubricating oil additive prepared by reacting fatty oil, diethanolamine and inorganic molybdenum compound. It has anti-wear and friction-reducing properties. It has been sold as a commodity by Vanderbilt Company under model 855.

U.S. Patent No. 5,137,647 discloses an organic molybdenum lubricating oil additive prepared by the reaction of fatty oil or acid, 2-(2-aminoethyl)aminoethanol and inorganic molybdenum compound, which has anti-wear, anti-friction, anti-oxidation, etc. performance.

US Patent No. 5,412,130 discloses a method for preparing an organic molybdenum lubricating oil additive by reacting diol, diamine, mercaptan and aminoethanol with an inorganic molybdenum compound.

U.S. Patent No. 6,046,263 discloses a multifunctional lubricating oil additive with anti-wear, anti-friction, and anti-oxidant properties, which is currently sold as a commodity by Ciba Company under the model F 10A.

However, some of the above-mentioned sulfur-free and phosphorus-free lubricating oil additive products have good anti-wear performance, but poor anti-friction performance; some have good anti-friction performance, but poor anti-wear performance; It works, and some mainly work in the state of boundary lubrication. Therefore, the development of lubricating oil additives with stronger anti-wear and anti-friction properties is still the direction of efforts of those skilled in the art.

Contents of the invention

The object of the present invention is to provide an organic molybdenum lubricating oil additive different from the prior art, which has better anti-wear and anti-friction properties.

Another object of the present invention is to provide a preparation method of the above organic molybdenum lubricating oil additive.

The organic molybdenum lubricating oil additive provided by the present invention is prepared by reacting the following three types of substances:

Polyol p-hydroxybenzoate;

Inorganic molybdenum compounds; and

Aliphatic amines, aromatic amines, mixed amines, amides or mixtures of any two or more of them.

The p-hydroxybenzoic acid polyol ester refers to the p-hydroxybenzoic acid polyol ester with shielding phenolic antioxidant group, which preferably has the following general formula:

或

or

Among them, at least one of X ₁ , X ₂ , and X ₃ is a group of structural formula (a), at least one of X ₄ , X ₅ , X ₆ , and X ₇ is a group of structural formula (a), and the remaining groups are may be the same or different, and are independently selected from H atoms, groups of formula (a) and groups of formula (b),

Wherein, R ₁ and R ₂ can be the same or different, and are independently selected from alkyl groups with 1 to 4 carbon atoms; n is an integer of 2 to 12; R ₃ is an H atom or a carbon atom number between 1 and 1 Saturated or unsaturated hydrocarbon groups between ～30.

Preferred materials with the above general formula (I), (II) include: 3,5-di-tert-butyl p-hydroxyphenylpropionate monoglyceride, 3,5-di-tert-butyl p-hydroxyphenylpropionate pentaerythritol ester, 3 -tert-butyl-5-methyl-p-hydroxyphenylpropionic acid, diglyceride of oleic acid, 3,5-di-tert-butyl-p-hydroxyphenylpropionic acid, diglyceride of oleic acid, 3,5-di-tert-butyl Diglyceryl p-hydroxyphenylpropionic acid, diglyceride of dodecanoic acid, 3,5-di-tert-butyl p-hydroxyphenylpropionic acid, diglyceride of stearic acid.

The inorganic molybdenum compound includes ammonium molybdate, sodium molybdate, molybdenum trioxide and/or mixtures thereof.

The fatty amine preferably has 4-30 carbon atoms, 1-5 amino groups, and a primary nitrogen atom and/or a secondary nitrogen atom.

The aromatic amine preferably has a side chain with 0-30 carbon atoms, 1-5 amino groups, and primary and/or secondary nitrogen atoms.

The mixed amine is preferably an organic amine having both the amino group of the aliphatic amine and the amino group of the aromatic amine.

The amides include amides with 2 to 60 carbon atoms and primary or secondary nitrogen atoms. More preferably, the amides are prepared by reacting fatty acids with organic amines with 1-6 amino groups and 1-30 carbon atoms or ammonia water. The fatty acid is preferably a saturated fatty acid and/or an unsaturated fatty acid with 1-30 carbon atoms. The organic amine is preferably diethanolamine, hydroxyethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine.

The organic molybdenum lubricating oil additive of the present invention is preferably prepared through the following steps:

Will account for 49-99% of the total weight of the reactant polyol ester of p-hydroxybenzoic acid, 0-50% of aliphatic amines, aromatic amines, mixed amines, amides or a mixture of any two or more of them, and 0.1-25% of the inorganic molybdenum compound is reacted to prepare the organic molybdenum lubricating oil additive product of the present invention.

The organic molybdenum lubricating oil additive of the present invention may be prepared with or without adding a solvent. When a solvent is added, optional solvents to be added include toluene, xylene, water, and the like. If a solvent is added, the solvent can be removed by means known to those skilled in the art after the reaction, such as under normal pressure or reduced pressure.

The reaction temperature range is between 60-160°C, preferably 100-130°C.

The reaction time is 1-10 hours, preferably 2-6 hours.

The reaction is preferably carried out under the protection of an inert gas, more preferably under the protection of nitrogen.

In the organic molybdenum lubricating oil additive prepared by the method of the present invention, the molybdenum content accounts for 0.1-8.0%, preferably 2.0-7.0%, of the total weight of the organic molybdenum lubricating oil additive.

It is obvious that those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope thereof. The technical solutions obtained by these changes and changes are all within the scope of the present invention. The description and examples of the invention are intended to be exemplary only, with a true scope and spirit of the invention being pointed out in the claims of this application.

Detailed ways

The organic molybdenum lubricating oil additive provided by the invention has excellent anti-wear and anti-friction properties. The present invention will be further described below by embodiment.

Example 1

Add 40g of 3-tert-butyl-5-methyl p-hydroxyphenylpropionate monoglyceride, 80ml of toluene, and 10g of DMF in a 250ml four-neck flask with a stirrer, thermometer, reflux condenser and feeder, under nitrogen protection Raise the temperature to 70-80°C. An aqueous solution made of 5 g of ammonium molybdate and 20 ml of distilled water was added dropwise, and the mixture was refluxed at 120° C. for 4 hours. The toluene was evaporated, and the slag was removed by filtration to obtain the organic molybdenum lubricating oil additive M-01, wherein the molybdenum content was 2.93% of the total weight of the organic molybdenum lubricating oil additive.

Example 2

In the 250ml four-necked bottle identical with embodiment 1, add dibutylamine 1g, F 10 A lubricating oil additive (Ciba company produces, commercially available, main component is 3,5-di-tert-butyl p-hydroxyphenyl propionate glyceride ) 40g, toluene 80ml, and heated up to 70-80°C under the protection of nitrogen. An aqueous solution made of 6 g of ammonium paramolybdate and 20 ml of distilled water was added dropwise, and the mixture was refluxed at 100° C. for 6 hours. The toluene was evaporated, and the slag was removed by filtration to obtain the organic molybdenum lubricating oil additive M-02, wherein the molybdenum content was 3.04% of the total weight of the organic molybdenum lubricating oil additive.

Example 3

Add 6g ammonium molybdate and 80g distilled water in the 250ml four-neck bottle identical with embodiment 1, add F 10 A lubricating oil additive (Ciba company produces, commercially available, main component is 3,5-di-tert-butyl p-hydroxybenzene Glyceryl propionate) 40g, DMF 5g, reflux reaction at 100°C for 6 hours under nitrogen protection. After the reaction was completed, the layers were allowed to stand and the water phase was removed. The moisture remaining in the oil phase was evaporated, and the slag was removed by filtration to obtain an organic molybdenum lubricating oil additive M-03, wherein the molybdenum content was 2.67% of the total weight of the organic molybdenum lubricating oil additive.

Example 4

In the same 250ml four-necked bottle as in Example 1, add laboratory-synthesized 3,5-di-tert-butyl p-hydroxyphenylpropionic acid, 40g of diglyceride of oleic acid, toluene 80ml, DMF10g, dibutylamine 2g, in Under nitrogen protection, the temperature was raised to 70-80°C. An aqueous solution made of 8 g of ammonium molybdate and 20 ml of distilled water was added dropwise, and the mixture was refluxed at 110° C. for 2 hours. The toluene was evaporated, and the slag was removed by filtration to obtain the organic molybdenum lubricating oil additive M-04, wherein the molybdenum content was 3.17% of the total weight of the organic molybdenum lubricating oil additive.

Example 5

In the same 250ml four-neck flask as in Example 1, add laboratory-synthesized 3,5-di-tert-butyl-p-hydroxyphenylpropionate pentaerythritol 40g, toluene 80ml, and the carbon number of side chain is 8 diphenylamine 1g, Under the protection of nitrogen, the temperature was raised to 70-80°C. An aqueous solution made of 4 g of ammonium molybdate and 10 ml of distilled water was added dropwise, and the mixture was refluxed at 120° C. for 2 hours. The toluene was evaporated, and the slag was removed by filtration to obtain the organic molybdenum lubricating oil additive M-05 of the present invention, wherein the molybdenum content was 1.03% of the total weight of the organic molybdenum lubricating oil additive.

Example 6

In the same 250ml four-necked bottle as in Example 1, add 40g of F 10 A lubricating oil additive and 80ml of toluene, and raise the temperature to 70-80°C under nitrogen protection. Add 3g of molybdenum trioxide, and reflux at 120°C for 2 hours. The toluene was evaporated, and the slag was removed by filtration to obtain the organic molybdenum lubricating oil additive M-06, wherein the molybdenum content was 0.24% of the total weight of the organic molybdenum lubricating oil additive.

Example 7

In the same 250ml four-neck bottle as in Example 1, add 3,5-di-tert-butyl p-hydroxyphenylpropionic acid, diglyceride 40g of oleic acid synthesized in the laboratory, oleic acid amide 10g prepared in the laboratory (from oil acid and hydroxyethylethylenediamine in a molar ratio of 1:1), and the temperature was raised to 70-80°C under the protection of nitrogen. An aqueous solution made of 10 g of ammonium molybdate and 20 ml of distilled water was added dropwise, and reacted at 110° C. for 4 hours. The organic molybdenum lubricating oil additive M-07 was obtained by filtering and removing the slag, wherein the molybdenum content was 5.35% of the total weight of the organic molybdenum lubricating oil additive.

Example 8

In the same 250ml four-necked bottle as in Example 1, add laboratory-synthesized 3,5-di-tert-butyl-p-hydroxyphenylpropionic acid, 25g of diglyceride of oleic acid, toluene 80ml, DMF20g, dibutylamine 2g, in Under nitrogen protection, the temperature was raised to 70-80°C. An aqueous solution made of 6 g of ammonium paramolybdate and 20 ml of distilled water was added dropwise, and the mixture was refluxed at 110° C. for 3 hours. The toluene was evaporated, and no residue was produced during the reaction process to obtain the organic molybdenum lubricating oil additive M-08, wherein the molybdenum content was 6.42% of the total weight of the organic molybdenum lubricating oil additive.

Example 9

In the same 250ml four-neck bottle as in Example 1, add 20g of diglyceride of 3,5-di-tert-butyl p-hydroxybenzoic acid and stearic acid synthesized in the laboratory, 80ml of toluene, 15g of laurylamide, dibutyl Add 2 g of amine and raise the temperature to 70-80°C under the protection of nitrogen. An aqueous solution made of 10 g of ammonium molybdate and 20 ml of distilled water was added dropwise, and the mixture was refluxed at 130° C. for 4 hours. The toluene was evaporated, and the slag was removed by filtration to obtain the organic molybdenum lubricating oil additive M-09, wherein the molybdenum content was 5.66% of the total weight of the organic molybdenum lubricating oil additive.

Example 10

The above-mentioned organic molybdenum lubricating oil additives M-01, M-02, M-04, M-08, commercially available F 10 A lubricating oil additives (produced by Ciba Company), Van 855 lubricating oil additives (produced by Vanderbilt Company), F 10 The mass ratio compound of A lubricating oil additive and Van 855 lubricating oil additive is compounded into 150SN base oil with the same dosage and common lubricating oil compound additive according to the same formula.

The anti-wear and anti-friction properties of each compound system obtained were measured by four-ball machine anti-wear and anti-friction evaluation test (industry standard SH/T0189-92). The test conditions are: temperature 75°C, rotation speed 1200 rpm, load 40Kg, test time 1 hour. The results are shown in Table 1 below. The data given by the anti-wear and anti-friction evaluation experiment of the four-ball machine include friction coefficient and wear scar diameter. The lower the wear scar diameter and friction coefficient, the better the anti-wear and anti-friction effect.

Table 1 Anti-wear and anti-friction test results of the compound system of the synthetic product and the control example

As can be seen from the test results in Table 1, the coefficient of friction produced by the organic molybdenum additive compound system of the present invention is smaller than that of the comparative example, and the diameter of the wear scar is smaller than that of the comparative example, indicating that the organic molybdenum lubricating oil additive provided by the present invention has excellent The anti-wear and anti-friction properties of the prior art.

Claims (21)

1. An organic molybdenum lubricating oil additive is characterized in that it is prepared by following material reaction: Polyol p-hydroxybenzoate; Inorganic molybdenum compounds; and Aliphatic amines, aromatic amines, mixed amines, amides or mixtures of any two or more of them. 2. according to the organic molybdenum lubricating oil additive of claim 1, it is characterized in that described p-hydroxyalkyl acid polyol ester has following general formula:

or

Among them, at least one of X ₁ , X ₂ , and X ₃ is a group of structural formula (a), at least one of X ₄ , X ₅ , X ₆ , and X ₇ is a group of structural formula (a), and the remaining groups are may be the same or different, and are independently selected from H atoms, groups of structural formula (a) and groups of structural formula (b);

Wherein, R ₁ and R ₂ can be the same or different, and are independently selected from alkyl groups with 1 to 4 carbon atoms; n is an integer of 2 to 12; R ₃ is an H atom or a carbon atom number between 1 and 1 Saturated or unsaturated hydrocarbon groups between ～30. 3. according to the organic molybdenum lubricating oil additive of claim 2, it is characterized in that said p-hydroxybenzoic acid polyhydric alcohol ester comprises 3,5-di-tert-butyl p-hydroxyphenyl propionate monoglyceride; 3,5-di Pentaerythritol tert-butyl-p-hydroxyphenylpropionate; diglyceride of 3-tert-butyl-5-methyl-p-hydroxyphenylpropionate, oleic acid; 3,5-di-tert-butyl-p-hydroxyphenylpropionate, oleic acid 3,5-di-tert-butyl-p-hydroxyphenylpropionic acid, diglyceride of dodecanoic acid or 3,5-di-tert-butyl-p-hydroxyphenylpropionic acid, diglyceride of stearic acid. 4. The organic molybdenum lubricating oil additive according to claim 1, characterized in that said inorganic molybdenum compound comprises ammonium molybdate, sodium molybdate, molybdenum trioxide and/or mixtures thereof. 5. The organic molybdenum lubricating oil additive according to claim 1, characterized in that the fatty amines include fats with 4 to 30 carbon atoms, 1 to 5 amino groups, and primary and/or secondary nitrogen atoms amine. 6. The organic molybdenum lubricating oil additive according to claim 1, characterized in that the aromatic amine comprises side chains with 0 to 30 carbon atoms, 1 to 5 amino groups with primary nitrogen and/or secondary nitrogen atoms Aromatic amines. 7. The organic molybdenum lubricating oil additive according to claim 1, characterized in that the mixed amines include aliphatic amino groups with 4 to 30 carbon atoms and 1 to 5 amino groups in the molecule and aliphatic amino groups with carbon atoms An arylamino group with 0-30 side chains and 1-5 amino groups. 8. The organic molybdenum lubricating oil additive according to claim 1, characterized in that said amides include amides with 2 to 60 carbon atoms and primary or secondary nitrogen atoms. 9. The organic molybdenum lubricating oil additive according to claim 8, characterized in that the amides are prepared by reacting fatty acids with organic amines with 1 to 6 nitrogen atoms and 1 to 30 carbon atoms or ammonia water. 10. The organic molybdenum lubricating oil additive according to claim 9, characterized in that the fatty acid is a saturated fatty acid and/or an unsaturated fatty acid with 1 to 30 carbon atoms. 11. The organic molybdenum lubricating oil additive according to claim 9, characterized in that said organic amine comprises diethanolamine, hydroxyethylethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. 12. The organic molybdenum lubricating oil additive according to claim 1, characterized in that it is prepared by the following steps: 49-99% p-hydroxybenzoic acid polyol ester, 0-50% fat The organic molybdenum lubricating oil additive product is prepared by reacting amines, aromatic amines, mixed amines, amides or mixtures of any two or more of them with 0.1-25% of inorganic molybdenum compounds. 13. according to the organic molybdenum lubricating oil additive of claim 1, it is characterized in that the preparation process of described organic molybdenum lubricating oil additive can also add solvent, the optional solvent that adds comprises toluene, xylene, water, under the situation of adding solvent , when the reaction is finished, the solvent can be distilled off under normal pressure or reduced pressure. 14. The organic molybdenum lubricating oil additive according to claim 1, characterized in that the temperature range of the reaction is between 60°C and 160°C. 15. The organic molybdenum lubricating oil additive according to claim 14, characterized in that the reaction temperature range is between 100°C and 130°C. 16. The organic molybdenum lubricating oil additive according to claim 1, characterized in that the reaction time is 1-10 hours. 17. The organic molybdenum lubricating oil additive according to claim 16, characterized in that the reaction time is 2-6 hours. 18. The organic molybdenum lubricating oil additive according to claim 1, characterized in that the reaction is carried out under the protection of an inert gas. 19. The method according to claim 18, characterized in that the inert gas is nitrogen. 20. The organic molybdenum lubricating oil additive according to any one of claims 1-19, characterized in that the molybdenum content therein accounts for 0.1-8.0% of the total weight of the lubricating oil additive. 21. The organic molybdenum lubricating oil additive according to claim 20, characterized in that the molybdenum content therein accounts for 2.0-7.0% of the total weight of the lubricating oil additive.